CN103262329A - Battery electrolyte solution containing certain ester-ased solvents, and batteries containing such an electrolyte solution - Google Patents

Battery electrolyte solution containing certain ester-ased solvents, and batteries containing such an electrolyte solution Download PDF

Info

Publication number
CN103262329A
CN103262329A CN2011800605511A CN201180060551A CN103262329A CN 103262329 A CN103262329 A CN 103262329A CN 2011800605511 A CN2011800605511 A CN 2011800605511A CN 201180060551 A CN201180060551 A CN 201180060551A CN 103262329 A CN103262329 A CN 103262329A
Authority
CN
China
Prior art keywords
ester
electrolyte solution
acetic acid
battery
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2011800605511A
Other languages
Chinese (zh)
Other versions
CN103262329B (en
Inventor
O·尤曾
D·M·韦尔什
D·R·威尔逊
R·B·珊卡
D·J·布伦南
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of CN103262329A publication Critical patent/CN103262329A/en
Application granted granted Critical
Publication of CN103262329B publication Critical patent/CN103262329B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Abstract

Battery electrolyte solutions contain certain ester solvents, a lithium salt and vinylene carbonate, vinyl ethylene carbonate or fluoroethylene carbonate. Batteries containing these solvents have excellent specific discharge capacities and reduced weight compared to batteries in which the electrolyte is based on ethylene carbonate.

Description

Contain some based on the cell electrolyte solution of the solvent of ester and the battery that contains such electrolyte solution
The application requires the priority of the U.S. Provisional Application submitted on December 15th, 2010 number 61/423,147.
The battery that the present invention relates to non-aqueous electrolytic solution and contain non-aqueous electrolytic solution.
Lithium battery is as the electronic equipment that once is widely used in vehicle and many types with secondary cell.These batteries have high energy and power density usually.Electrolyte solution in the lithium battery must be non-aqueous type.Non-aqueous electrolytic solution generally is the solution of lithium salts in the organic solvent with high-k or ORGANIC SOLVENT MIXTURES.
Solvent must satisfy many requirements, and therefore the dicyandiamide solution of having found with practical use is considerably less.Any candidate's solvent must satisfy some basic demands.These are included in the whole operation temperature range and lithium salts are maintained in the solution high-k, the chemical stability in the presence of all the other components of solution, and the electrochemical stability in operating voltage range.In addition, solvent must be low-vapor pressure liquid in wide temperature range; The useful operating temperature range of battery is subjected to the fusing point of dicyandiamide solution (or its component) and the restriction of boiling point usually.
Although above-mentioned standard is the essential attribute of any practical solvent system, they fully are not limited to the dicyandiamide solution that the lithium cell electrolyte solution neutral can be good.Though many dicyandiamide solutions have all these attributes, performance is good inadequately.Therefore, all practical lithium cell electrolyte solution all are based on small amount of carbon ester compound for example ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate and ethylmethyl carbonate basically.At present, the mixture of ethylene carbonate and ethylene carbonate and diethyl carbonate and/or ethylmethyl carbonate is the most general so far dicyandiamide solution.
The main cause of selecting carbonate solvent is that they form stable solid electrolyte interface (SEI) layer at the graphite anode place of lithium battery.The key component of SEI layer is solvent and the salt that decomposes.The SEI layer forms in the initial charge circulation of battery.Therefore, except every other essential attribute, organic solvent must be able to form the SEI layer of stablizing and function being arranged.The SEI layer must be electronic isolation, but allows lithium ion with regard to the meaning of its migration with regard to the SEI layer, and it is ionic conductivity.The formation of SEI layer is crucial for battery performance.If do not form the SEI layer, if perhaps the SEI layer is not tight or unstable, battery will move bad, if not the words of not moving fully.Even between carbonate solvent, SEI forms and also has very big-difference.Ethylene carbonate is that good relatively SEI forms agent (former), but other carbonic esters are weaker.Usually in these solution based on carbonic ester, comprise the additive that further enhancing SEI forms.Attempted some compounds are promoted additive as SEI in based on the dicyandiamide solution of carbonic ester, obtained success in various degree.
Critical limitation based on the dicyandiamide solution of carbonic ester is operating temperature.This solidifies ethylene carbonate in 37 ℃, and self almost can not be used as solvent, because it is solid or thick liquid in the normal running temperature scope of great majority application.Therefore, must add other materials to reduce setting temperature and to allow wideer operating temperature range to ethylene carbonate usually.Therefore, diethyl carbonate exists as cosolvent usually.Even ethylene carbonate/diethyl carbonate dicyandiamide solution ,-20 ℃ or more also become under the low temperature very thickness or even solidify, it causes bad by electrolytical ion transportation and loss battery performance.This bad cryogenic property is to use (for example vehicle) or battery out of doors to be exposed to the major limitation of using these batteries in cold other application (for example space vehicle).
In addition, ethylene carbonate can release of carbon dioxide in charging cycle, and it can cause that battery size changes (expansion).When ethylene carbonate decomposes in charging cycle, emit the heat of significant quantity, this has reduced battery life also is safety concerns simultaneously.In order to expand operable temperature range, with ethylene carbonate and dialkyl carbonate combination, it has the flash-point lower than expection usually.
Also proposed to contain the dicyandiamide solution of other materials.In those other materials, comprise some ester compounds.Proposed some ester compounds is used as cosolvent in the dicyandiamide solution based on carbonic ester, be lower than-20 ℃ to attempt operating temperature range expanded to.Reach in the list of references of wherein quoting at U.S.'s publication application number 2009/0253046, described the several method along this thinking.Wherein, some certain esters compound is incorporated in ethylene carbonate/ethylmethyl carbonate dicyandiamide solution with the difference amount.The ester compounds of describing in US 2009/0253046 is methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate and butyl butyrate.US 2009/0253046 has described and used for example attempting more in early days of methyl formate, methyl acetate and ethyl acetate of other ester classes in the multicomponent electrolyte preparations, and stated that those ester solvents do not produce good rate capability (rate capacity) at a lower temperature, and when being higher than 25 ℃, do not show good restoring force, even when mixing with carbonate solvent.
U.S. Patent number 6,492,064 has described the lithium cell electrolyte solvent that contains ethylene carbonate, dimethyl carbonate and methyl acetate, and other solvents that contain ethylene carbonate, dimethyl carbonate, diethyl carbonate and alkyl or fluoro-alkyl ester compounds.
US publication application number 2008-0241699 has proposed 5 kinds of specific ester as the solvent for lithium ion battery electrolyte according to the standard aspect chemical stability in the presence of lithium salts, big electrochemical stability windows, fusing point, viscosity, boiling point, flash-point, vapour pressure and the cost.These ester classes are gamma-valerolactone, isobutyryl methyl acetate, acetic acid 2-methoxy ethyl ester, acetic acid 2-ethoxyethyl group ester and diethy-aceto oxalate.Yet, US 2008-0241699 does not describe any battery that uses such ester class to make as electrolyte solvent, and do not indicate any these 5 kinds of specific ester whether or under which kind of condition, can form the stable SEI layer, and therefore can in fact successfully work as the lithium cell electrolyte solvent.As follows, in them at least three kinds can not be as electrolyte solvent, even when forming the agent blending with the known electrolyte solvent of another kind and SEI.US 2008-0241699 has proposed ethylene carbonate and described ester compounds blending are formed agent as SEI.
Desired is a kind of dicyandiamide solution for lithium cell electrolyte solution, and described dicyandiamide solution is from ℃ working at least 40 ℃ temperature range at least-30, and forms the stable SEI layer, therefore allows to obtain good battery performance.
On the one hand, the present invention relates to a kind of non-aqueous batteries electrolyte solution, it comprises:
(1) at least a lithium salts, its amount provides the described lithium salt solution of 0.1M at least in described cell electrolyte solution,
(2) at least a have the ether ester compound of maximum 12 carbon atoms, at least a mono alkyl ester compound or its mixture with maximum 8 carbon atoms, described lithium salts solubilized therein arrives at least 0.1 mole every liter degree, wherein said ether ester compound or mono alkyl ester compound can partially or completely be fluoridized, and
(3) based on the combined wt of component (2) and (3), 0.5 to 20wt.% vinylene carbonate, 4-vinyl-1,3-dioxolanes-2-ketone, carbonic acid fluorinated ethylene ester or its any two or more kinds of mixtures.
The invention still further relates to a kind of battery, it comprises anode, negative electrode, be configured between described anode and the negative electrode dividing plate and with the electrolyte solution of described anode and the contacted the invention described above of negative electrode.
The applicant has been found that vinylene carbonate, 4-vinyl-1, and the combination of 3-dioxolanes-2-ketone and/or carbonic acid fluoro ethyl ester and these ester solvents provides outstanding battery performance.Even when only comprising (if comprising) a small amount of non-halogenated cycloalkyl ester of carbonic acid and the non-halogenated straight chain dialkyl of carbonic acid solvent at cell electrolyte solution, situation also is like this.As if having a small amount of vinylene carbonate, 4-vinyl-1 in cell electrolyte solution of the present invention, 3-dioxolanes-2-ketone and/or carbonic acid fluoro ethyl ester cause forming the SEI layer of stablizing and function being arranged.This result is astonishing, because in existing lithium battery, the formation of SEI mainly depends on for example existence of ethylene carbonate or propene carbonate of the non-halogenated cycloalkyl ester compound of carbonic acid.In addition, the applicant has been found that known can be used for can not enough work with these ester solvents, unless have a large amount of ethylene carbonates or propene carbonate well based on other SEI promoter in the dicyandiamide solution of ethylene carbonate or propene carbonate.
Therefore, the invention provides a kind of mode, by described mode, can substitute most of or whole ethylene carbonate, propene carbonate and dialkyl carbonate with some ester solvent.Therefore, in a preferred embodiment, cell electrolyte solution contains the weight based on solution, be no more than 30%, preferably be no more than 20%, more preferably no more than the non-halogenated alkylene ester of 10% carbonic acid for example ethylene carbonate or propene carbonate and/or the non-halogenated straight chain dialkyl of carbonic acid or its mixture, and can not contain these materials.
The present invention allows people that the potential benefit that provides of these ester solvents is provided in simple formulations, particularly good cryogenic property.Described cell electrolyte solution also provides other advantages, for example than produce based on the lower bulk density of the electrolyte solution of ethylene carbonate, few gas and than many based on the higher flash-point of the electrolyte of ethylene carbonate.Many described ester compounds discharge after decomposition than ethylene carbonate less heat, and this further helps battery life and fail safe.Described cell electrolyte solution is also stable under high voltage, allows to make up to have up to 5V or more high-tension battery.
In other respects, the present invention relates to a kind of non-aqueous batteries electrolyte solution, it comprises:
(1) at least a lithium salts, its amount provides the described lithium salt solution of 0.1M at least in described cell electrolyte solution, and
(2) have acetic acid 2-alkoxyl-1-alkyl ethyl ester or the acetic acid 2-alkoxyl-2-alkyl ethyl ester of maximum 12 carbon atoms, wherein said alkoxyl contains 1 to 7, preferred 1 to 3, more preferably 1 or 2 carbon atom and can be by fluoro partially or completely, and wherein said alkyl contains 1 to 7, preferred 1 to 3, more preferably 1 or 2 carbon atom and can be by fluoro partially or completely, and the amount of described ester is enough to dissolve described lithium salts.The invention still further relates to a kind of battery, it comprises anode, negative electrode, be configured between described anode and the negative electrode dividing plate and with described anode and the contacted this cell electrolyte solution of negative electrode.
Acetic acid 2-alkoxyl-1-alkyl ethyl ester and acetic acid 2-alkoxyl-2-alkyl ethyl ester compound is the particularly advantageous solvent for non-aqueous electrolytic solution.These materials provide good battery performance in wide temperature range, even do not exist or exist hardly the non-halogenated alkylene ester compound of carbonic acid for example under the situation of ethylene carbonate and propene carbonate and the non-halogenated dialkyl compound of carbonic acid.Acetic acid 2-alkoxyl-1-alkyl ethyl ester and acetic acid 2-alkoxyl-2-alkyl ethyl ester compound has high-flash, low-freezing, and discharges than ethylene carbonate less heat when they decompose in the battery charge circulation.Acetic acid 2-alkoxyl-1-alkyl ethyl ester and acetic acid 2-alkoxyl-2-alkyl ethyl ester compound also has the bulk density more much lower than ethylene carbonate, so their use can cause the remarkable reduction of battery weight.Another advantage of acetic acid 2-alkoxyl-1-alkyl ethyl ester and acetic acid 2-alkoxyl-2-alkyl ethyl ester is, described cell electrolyte solution and the battery that contains described electrolyte solution (for example based on the weight of described cell electrolyte solution, are up to 1000ppm or more water) in the presence of low amounts of water more stable.The cell electrolyte solution based on ethylene carbonate that shows the capability retention loss when containing the water that is low to moderate 50ppm when solution is different, even the battery that contains cell electrolyte solution of the present invention up to 1000ppm water or more for a long time, also shows outstanding capability retention at water content.
In other respects, the present invention relates to a kind of non-aqueous batteries electrolyte solution, it comprises:
(1) at least a lithium salts, its amount provides the described lithium salt solution of 0.1M at least in described cell electrolyte solution, and
(2) by the ether ester compound of structure I and any expression of II, wherein structure I is
Figure BPA00001735175400061
R wherein 1Be hydrogen, have straight or branched alkyl or a R of 1 to 5 carbon atom 4-O-R 5-group, wherein R 4Be alkyl, R 5Be alkylidene, and R 4And R 5Lump together and have maximum 5 carbon atoms, R 2Be the straight or branched alkylidene with 1 to 7 carbon atom, R 3Be the branched-chain or straight-chain alkyl with 1 to 3 carbon atom, wherein R 1, R 2And R 3Lump together and have maximum 12 carbon atoms, and R 1, R 2And R 3In at least one fluoridized by at least part of,
Structure I I is
R wherein 6Be hydrogen, have straight or branched alkyl or a R of 1 to 6 carbon atom 8-O-R 9-group, wherein R 8Be alkyl, R 9Be alkylidene, and R 8And R 9Lump together and have maximum 6 carbon atoms, R 7Be the straight or branched alkyl with maximum 6 carbon atoms, wherein R 6And R 7In at least one fluoridized by at least part of, and in addition, R wherein 6And R 7Lump together and have maximum 7 carbon atoms.The invention still further relates to a kind of battery, it comprises anode, negative electrode, be configured between described anode and the negative electrode dividing plate and with described anode and the contacted this cell electrolyte solution of negative electrode.
Fig. 1 is the figure of the discharge curve that circulates fully of two kinds of batteries of the present invention (embodiment 1 and 2) and control cell (control cell A).
Fig. 2 is the figure of the cycle performance discharge curve of battery of the present invention (embodiment 1) and two kinds of control cell (control cell A and B).
Fig. 3 is the figure of the discharge curve that circulates fully of 5 kinds of batteries of the present invention (embodiment 3A to 3E) and two kinds of control cell (control cell A and B).
Fig. 4 is the figure of the discharge curve that circulates fully of battery of the present invention (embodiment 4) and control cell (control cell A).
Fig. 5 is the figure of the discharge curve that circulates fully of two kinds of batteries of the present invention (embodiment 5 and 6) and 4 kinds of control cell (control cell A, C, D and E).
Fig. 6 is the figure of the discharge curve that circulates fully of 5 kinds of control cell (control cell A, G, H, I and J).
Fig. 7 is the figure of the discharge curve that circulates fully of three kinds of batteries of the present invention (embodiment 7,8 and 9) and control cell (control cell A).
Fig. 8 is the figure of the discharge curve that circulates fully of three kinds of batteries of the present invention ( embodiment 10,11 and 12) and 6 kinds of control cell (control cell A, K, L, M, N and O).
Fig. 9 is the figure of the discharge curve that circulates fully of 4 kinds of control cell (control cell A, P1, P2 and P3).
Figure 10 is the figure of the discharge curve that circulates fully of three kinds of batteries of the present invention ( embodiment 13,14 and 15) and three kinds of control cell (control cell A, Q1 and Q2).
Figure 11 is the figure of the discharge curve that circulates fully of 4 kinds of control cell (control cell A, R1, R2 and R3).
Figure 12 is the figure of the discharge curve that circulates fully of two kinds of batteries of the present invention (embodiment 16 and 17) and two kinds of control cell (control cell A and S).
Lithium salts can be any lithium salts that is fit to battery applications, comprises for example LiAsF of lithium salts 6, LiPF 6, LiPF 4(C 2O 4), LiPF 2(C 2O 4) 2, LiBF 4, LiB (C 2O 4) 2, LiBF 2(C 2O 4), LiClO 4, LiBrO 4, LiIO 4, LiB (C 6H 5) 4, LiCH 3SO 3, LiN (SO 2C 2F 5) 2And LiCF 3SO 3LiPF 6, LiPF 4(C 2O 4), LiBF 4, LiB (C 2O 4) 2, LiCF 3SO 3And LiN (SO 2CF 3) 2Be preferred type, LiPF 6It is particularly preferred lithium salts.Also can use any two or more kinds of mixtures of above-mentioned lithium salts.
The lithium salt of cell electrolyte solution is at least 0.1 mol (0.1M), preferably at least 0.5 mol (0.5M), more preferably at least 0.75 mol (0.75M), preferably the highest 3 mol (3.0M), more preferably the highest 1.5 mol (1.5M).
Cell electrolyte solution contains at least a ether ester compound and/or at least a mono alkyl ester compound with maximum 8 carbon atoms with maximum 12 carbon atoms, and lithium salts solubilized in described ester compounds arrives the degree of at least 0.1 mole of every liter of ester compounds.Described ether ester compound or mono alkyl ester compound can partially or completely be fluoridized, and this means that some or all of (under the situation of the fluoridizing fully) hydrogen with carbon atom bonding can be replaced by fluorine.
Ether ester compound can be represented by structure I
Figure BPA00001735175400091
R wherein 1Be hydrogen, have straight or branched alkyl or a R of 1 to 5 carbon atom 4-O-R 5-group, wherein R 4Be alkyl, R 5Be alkylidene, and R 4And R 5Lump together and have maximum 5 carbon atoms.R 2Be the straight or branched alkylidene with 1 to 7 carbon atom, R 3It is the branched-chain or straight-chain alkyl with 1 to 3 carbon atom.R 1, R 2And R 3Lump together and have maximum 12 carbon atoms, preferred maximum 9 carbon atoms, more preferably maximum 7 carbon atoms.R 1, R 2And R 3In any or all can partially or completely be fluoridized.
R 1Be preferably the straight chained alkyl with 1 to 3 carbon atom, it can partially or completely be fluoridized.R 1Most preferably be methyl, ethyl, fluoro methyl, difluoromethyl or trifluoromethyl.
R 2Be preferably the straight-chain alkyl-sub-with 2 to 3 carbon atoms, it can partially or completely be fluoridized.R 2Most preferably be ethylidene (CH 2-CH 2-), 2-methyl ethylidene (CH 2-CH (CH 3)-), 1-methyl ethylidene (CH (CH 3)-CH 2-), propylidene (CH 2-CH 2-CH 2-) or 2,2-difluoro propylidene (CH 2-CF 2-CH 2-).
R 3Be preferably the straight chained alkyl with 1 to 3 carbon atom, it can be the straight or branched alkyl of partially or completely being fluoridized with 1 to 3 carbon atom.R 3More preferably contain 1 or 2 carbon atom.R 3Most preferably be methyl, ethyl, 2-fluoro ethyl, 2,2-two fluoro ethyls or 2,2,2-trifluoroethyl.
Preferred ether ester compound comprises the acetic acid 2-alkoxyethyl ester with maximum 12 carbon atoms, acetic acid 2-alkoxyl-1-alkyl ethyl ester and acetic acid 2-alkoxyl-2-alkyl ethyl ester, acetic acid 2-methoxy ethyl ester for example, acetic acid 2-ethoxyethyl group ester, acetic acid 2-methoxyl group-1-Methylethyl ester, acetic acid 2-methoxyl group-2-Methylethyl ester, acetic acid 2-ethyoxyl-1-Methylethyl ester, acetic acid 2-ethyoxyl-2-Methylethyl ester, acetic acid 2-(2,2, the 2-trifluoro ethoxy)-ethyl ester, acetic acid 2-(2,2, the 2-trifluoro ethoxy)-1-Methylethyl ester, acetic acid 2-(2,2, the 2-trifluoro ethoxy)-2-Methylethyl ester, fluoro acetic acid 2-methoxy ethyl ester, fluoro acetic acid 2-ethoxyethyl group ester, fluoro acetic acid 2-methoxyl group-1-Methylethyl ester, fluoro acetic acid 2-methoxyl group-2-Methylethyl ester, fluoro acetic acid 2-ethyoxyl-1-Methylethyl ester, fluoro acetic acid 2-ethyoxyl-2-Methylethyl ester, fluoro acetic acid 2-(2,2, the 2-trifluoro ethoxy)-ethyl ester, difluoroacetic acid 2-methoxy ethyl ester, difluoroacetic acid 2-ethoxyethyl group ester, difluoroacetic acid 2-methoxyl group-1-Methylethyl ester, difluoroacetic acid 2-methoxyl group-2-Methylethyl ester, difluoroacetic acid 2-ethyoxyl-1-Methylethyl ester, difluoroacetic acid 2-ethyoxyl-2-Methylethyl ester, difluoroacetic acid 2-(2,2, the 2-trifluoro ethoxy)-ethyl ester, trifluoroacetic acid 2-methoxy ethyl ester, trifluoroacetic acid 2-ethoxyethyl group ester, trifluoroacetic acid 2-methoxyl group-1-Methylethyl ester, trifluoroacetic acid 2-methoxyl group-2-Methylethyl ester, trifluoroacetic acid 2-ethyoxyl-1-Methylethyl ester, trifluoroacetic acid 2-ethyoxyl-2-Methylethyl ester or trifluoroacetic acid 2-(2,2, the 2-trifluoro ethoxy)-ethyl ester, or its two or more mixture.
Other useful ether ester compounds comprise propionic acid 2-methoxy ethyl ester, propionic acid 2-ethoxyethyl group ester, propionic acid 2-methoxyl group-1-Methylethyl ester, propionic acid 2-ethyoxyl-1-Methylethyl ester, propionic acid 2-methoxyl group-2-Methylethyl ester, propionic acid 2-ethyoxyl-2-Methylethyl ester, propionic acid 2-(2,2,2-trifluoro ethoxy)-ethyl ester, propionic acid 2-(2,2,2-trifluoro ethoxy)-1-Methylethyl ester, propionic acid 2-(2,2, the 2-trifluoro ethoxy)-2-Methylethyl ester, 2-fluorine propionic acid 2-methoxy ethyl ester, 2-fluorine propionic acid 2-ethoxyethyl group ester, 2-fluorine propionic acid 2-methoxyl group-1-Methylethyl ester, 2-fluorine propionic acid 2-ethyoxyl-1-Methylethyl ester, 2-fluorine propionic acid 2-methoxyl group-2-Methylethyl ester, 2-fluorine propionic acid 2-ethyoxyl-2-Methylethyl ester, 2,2-difluoro propionic acid 2-methoxy ethyl ester, 2,2-difluoro propionic acid 2-ethoxyethyl group ester, 2,2-difluoro propionic acid 2-methoxyl group-1-Methylethyl ester, 2,2-difluoro propionic acid 2-ethyoxyl-1-Methylethyl ester, 3-fluorine propionic acid 2-methoxy ethyl ester, 3-fluorine propionic acid 2-ethoxyethyl group ester, 3-fluorine propionic acid 2-methoxyl group-1-Methylethyl ester, 3-fluorine propionic acid 2-ethyoxyl-1-Methylethyl ester, 3-fluorine propionic acid 2-methoxyl group-2-Methylethyl ester, 3-fluorine propionic acid 2-ethyoxyl-2-Methylethyl ester, 3,3-difluoro propionic acid 2-methoxy ethyl ester, 3,3-difluoro propionic acid 2-ethoxyethyl group ester, 3,3-difluoro propionic acid 2-methoxyl group-1-Methylethyl ester, 3,3-difluoro propionic acid 2-ethyoxyl-1-Methylethyl ester, 3,3-difluoro propionic acid 2-methoxyl group-2-Methylethyl ester, 3,3-difluoro propionic acid 2-ethyoxyl-2-Methylethyl ester, 3,3,3-trifluoroacetic acid 2-methoxy ethyl ester, 3,3,3-trifluoroacetic acid 2-ethoxyethyl group ester, 3,3,3-trifluoroacetic acid 2-methoxyl group-1-Methylethyl ester, 3,3,3-trifluoroacetic acid 2-ethyoxyl-1-Methylethyl ester, 3,3,3-trifluoroacetic acid 2-methoxyl group-2-Methylethyl ester, 3,3,3-trifluoroacetic acid 2-ethyoxyl-2-Methylethyl ester, 2,3,3,3-tetrafluoro propionic acid 2-methoxy ethyl ester, 2,3,3,3-tetrafluoro propionic acid 2-ethoxyethyl group ester, 2,3,3,3-tetrafluoro propionic acid 2-methoxyl group-1-Methylethyl ester, 2,3,3,3-tetrafluoro propionic acid 2-ethyoxyl-1-Methylethyl ester, 2,3,3,3-tetrafluoro propionic acid 2-methoxyl group-2-Methylethyl ester, 2,3,3,3-tetrafluoro propionic acid 2-ethyoxyl-2-Methylethyl ester, 2-methoxyacetic acid 2-methoxy ethyl ester, 2-methoxyacetic acid 2-ethoxyethyl group ester, 2-ethoxyacetic acid 2-methoxy ethyl ester, 2-ethoxyacetic acid 2-ethoxyethyl group ester, 2-methoxypropionic acid 2-methoxy ethyl ester, 2-methoxypropionic acid 2-ethoxyethyl group ester, 2-ethoxy-propionic acid 2-methoxy ethyl ester, 2-ethoxy-propionic acid 2-ethoxyethyl group ester, 2,2-difluoro propionic acid 2-methoxyl group-2-Methylethyl ester, 2,2-difluoro propionic acid 2-ethyoxyl-2-Methylethyl ester, 2-methoxyacetic acid 2-methoxyl group-1-Methylethyl ester, 2-methoxyacetic acid 2-ethyoxyl-1-Methylethyl ester, 2-methoxyacetic acid 2-methoxyl group-2-Methylethyl ester, 2-methoxyacetic acid 2-ethyoxyl-2-Methylethyl ester, 2-ethoxyacetic acid 2-methoxyl group-1-Methylethyl ester, 2-ethoxyacetic acid 2-ethyoxyl-1-Methylethyl ester, 2-ethoxyacetic acid 2-methoxyl group-2-Methylethyl ester, 2-ethoxyacetic acid 2-ethyoxyl-2-Methylethyl ester, 2-methoxypropionic acid 2-methoxyl group-1-Methylethyl ester, 2-methoxypropionic acid 2-ethyoxyl-1-Methylethyl ester, 2-methoxypropionic acid 2-methoxyl group-2-Methylethyl ester, 2-methoxypropionic acid 2-ethyoxyl-2-Methylethyl ester, 2-ethoxy-propionic acid 2-methoxyl group-1-Methylethyl ester, 2-ethoxy-propionic acid 2-ethyoxyl-1-Methylethyl ester, 2-ethoxy-propionic acid 2-methoxyl group-2-Methylethyl ester, 2-ethoxy-propionic acid 2-ethyoxyl-2-Methylethyl ester, 2-methoxyacetic acid 2-(2,2,2-trifluoro ethoxy) ethyl ester, 2-(2,2, the 2-trifluoro ethoxy) acetic acid 2-methoxy ethyl ester, 2-ethoxyacetic acid 2-(2,2,2-trifluoro ethoxy) ethyl ester, 2-(2,2, the 2-trifluoro ethoxy) acetic acid 2-ethoxyethyl group ester, 2-methoxypropionic acid 2-(2,2,2-trifluoro ethoxy) ethyl ester, 2-(2,2, the 2-trifluoro ethoxy) propionic acid 2-methoxy ethyl ester, 2-ethoxy-propionic acid 2-(2,2,2-trifluoro ethoxy) ethyl ester, 2-(2,2, the 2-trifluoro ethoxy) propionic acid 2-ethoxyethyl group ester, 2-methoxyacetic acid 2-(2,2,2-trifluoro ethoxy)-1-Methylethyl ester, 2-methoxyacetic acid 2-(2,2, the 2-trifluoro ethoxy)-2-Methylethyl ester, 2-(2,2,2-trifluoro ethoxy) acetic acid 2-methoxyl group-1-Methylethyl ester, 2-ethoxyacetic acid 2-(2,2, the 2-trifluoro ethoxy)-1-Methylethyl ester, 2-(2,2,2-trifluoro ethoxy) acetic acid 2-ethyoxyl-1-Methylethyl ester, 2-(2,2, the 2-trifluoro ethoxy) acetic acid 2-(2,2,2-trifluoro ethoxy)-1-Methylethyl ester, 2-(2,2, the 2-trifluoro ethoxy) acetic acid 2-methoxyl group-2-Methylethyl ester, 2-ethoxyacetic acid 2-(2,2,2-trifluoro ethoxy)-2-Methylethyl ester, 2-(2,2, the 2-trifluoro ethoxy) acetic acid 2-ethyoxyl-2-Methylethyl ester, 2-(2,2,2-trifluoro ethoxy) acetic acid 2-(2,2, the 2-trifluoro ethoxy)-2-Methylethyl ester, 2-methoxypropionic acid 2-(2,2,2-trifluoro ethoxy)-1-Methylethyl ester, 2-methoxypropionic acid 2-(2,2, the 2-trifluoro ethoxy)-2-Methylethyl ester, 2-(2,2,2-trifluoro ethoxy) propionic acid 2-methoxyl group-1-Methylethyl ester, 2-ethoxy-propionic acid 2-(2,2, the 2-trifluoro ethoxy)-1-Methylethyl ester, 2-(2,2,2-trifluoro ethoxy) propionic acid 2-ethyoxyl-1-Methylethyl ester, 2-(2,2, the 2-trifluoro ethoxy) propionic acid 2-(2,2,2-trifluoro ethoxy)-1-Methylethyl ester, 2-(2,2, the 2-trifluoro ethoxy) propionic acid 2-methoxyl group-2-Methylethyl ester, 2-ethoxy-propionic acid 2-(2,2,2-trifluoro ethoxy)-2-Methylethyl ester, 2-(2,2, the 2-trifluoro ethoxy) propionic acid 2-ethyoxyl-2-Methylethyl ester, 2-(2,2,2-trifluoro ethoxy) propionic acid 2-(2,2,2-trifluoro ethoxy)-2-Methylethyl ester etc.
The mono alkyl ester compound can be represented by structure I I
Figure BPA00001735175400131
R wherein 6Straight or branched alkyl or the R with 1 to 6 carbon atom that are hydrogen, can be partially or completely fluoridized 8-O-R 9-group, wherein R 8Be alkyl, R 9Be alkylidene, and R 8And R 9Lump together and have maximum 6 carbon atoms, and R 7It is the straight or branched alkyl with maximum 6 carbon atoms that partially or completely to be fluoridized.R 6And R 7Lump together and have maximum 7 carbon atoms, and preferably lump together and contain 3 to 6 carbon atoms.R 6Preferably contain at least one carbon atom.
The mono alkyl ester examples for compounds that is fit to comprises methyl formate, Ethyl formate, propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, isobutyl acetate, butyl acetate, pentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, isobutyl propionate, butyl propionate, amyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, methyl valerate, ethyl valerate, ethyl isovalerate, ethyl hexanoate, methyl caproate, formic acid 2,2,2-trifluoroethyl ester, acetic acid 2,2,2-trifluoroethyl ester, propionic acid 2,2,2-trifluoroethyl ester, butyric acid 2,2,2-trifluoroethyl ester, valeric acid 2,2,2-trifluoroethyl ester, isovaleric acid 2,2,2-trifluoroethyl ester, caproic acid 2,2,2-trifluoroethyl ester, the fluoro methyl acetate, fluoro ethyl acetate, the fluoro propyl acetate, the fluoro butyl acetate, the fluoro pentyl acetate, the fluoro hexyl acetate, 2,2-difluoro methyl propionate, 2,2-difluoro ethyl propionate, 2,2-difluoro propyl propionate, 2,2-difluoro butyl propionate, 2,2-difluoro amyl propionate, 3,3,3-trifluoroacetic acid methyl esters, 3,3,3-trifluoroacetic acid ethyl ester, 3,3,3-trifluoroacetic acid propyl ester, 3,3,3-trifluoroacetic acid butyl ester, 3,3,3-trifluoroacetic acid pentyl ester, 2,2-difluoro methyl butyrate, 2,2-difluoro ethyl butyrate, 2,2-difluoro propyl butyrate, methyl valerate, ethyl valerate, ethyl isovalerate, ethyl hexanoate, methyl caproate, the 2-methoxy menthyl acetate, 2-methoxyacetic acid ethyl ester, 2-methoxyacetic acid propyl ester, 2-methoxyacetic acid isopropyl ester, 2-methoxyacetic acid butyl ester, the 2-ethoxy acetate, the 2-ethoxy ethyl acetate, 2-ethoxyacetic acid propyl ester, 2-ethoxyacetic acid isopropyl ester, 2-ethoxyacetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl isopropyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c isopropyl propionate, 2-ethoxy-propionic acid butyl ester, 2-methoxyacetic acid (2,2, the 2-trifluoroethyl) ester, 2-methoxyacetic acid 2,2-difluoro propyl diester, 2-methoxyacetic acid (2,2, the 2-trifluoro)-1-Methylethyl ester, 2-methoxyacetic acid (2,2,2-trifluoro)-1-(trifluoromethyl) ethyl ester, 2-methoxyacetic acid 2-fluorine butyl ester, 2-methoxyacetic acid 2,2-difluoro butyl ester, 2-(2,2, the 2-trifluoro ethoxy) methyl acetate, 2-(2,2,2-trifluoro ethoxy) methyl acetate, 2-ethoxyacetic acid (2,2, the 2-trifluoro ethoxy) ester, 2-(2,2,2-trifluoro ethoxy) ethyl acetate, 2-(2,2, the 2-trifluoro ethoxy) acetic acid (2,2,2-trifluoro ethoxy) ester, 2-(2,2, the 2-trifluoro ethoxy) propyl acetate, 2-(2,2,2-trifluoro ethoxy) isopropyl acetate, 2-ethoxyacetic acid (2,2, the 2-trifluoro)-1-Methylethyl ester, 2-ethoxyacetic acid (2,2,2-trifluoro)-1-(trifluoromethyl) ethyl ester, 2-(2,2, the 2-trifluoro ethoxy) butyl acetate, 2-ethoxyacetic acid 2-fluorine butyl ester, 2-ethoxyacetic acid 2,2-difluoro butyl ester, 2-methoxypropionic acid (2,2, the 2-trifluoroethyl) ester, 2-methoxypropionic acid 2,2-difluoro propyl diester, 2-methoxypropionic acid (2,2,2-trifluoro)-1-Methylethyl ester, 2-methoxypropionic acid (2,2, the 2-trifluoro)-1-(trifluoromethyl) ethyl ester, 2-methoxypropionic acid 2-fluorine butyl ester, 2-methoxypropionic acid 2,2-difluoro butyl ester, 2-(2,2, the 2-trifluoro ethoxy) methyl propionate, 2-(2,2,2-trifluoro ethoxy) methyl propionate, 2-ethoxy-propionic acid (2,2, the 2-trifluoro ethoxy) ester, 2-(2,2,2-trifluoro ethoxy) ethyl propionate, 2-(2,2, the 2-trifluoro ethoxy) propionic acid (2,2,2-trifluoro ethoxy) ester, 2-(2,2, the 2-trifluoro ethoxy) propyl propionate, 2-(2,2,2-trifluoro ethoxy) isopropyl propionate, 2-ethoxy-propionic acid (2,2, the 2-trifluoro)-1-Methylethyl ester, 2-ethoxy-propionic acid (2,2,2-trifluoro)-1-(trifluoromethyl) ethyl ester, 2-(2,2, the 2-trifluoro ethoxy) butyl propionate, 2-ethoxy-propionic acid 2-fluorine butyl ester, 2-ethoxy-propionic acid 2,2-difluoro butyl ester etc.Can use the mixture of two or more ether ester compounds and/or mono alkyl ester compound.
In general, ether ester compound or mono alkyl ester compound preferably contain be less than 2000ppm, preferably be less than 1000ppm, more preferably less than 200ppm, more preferably less than 50ppm even more preferably no more than the water of 30ppm and each of alcohol compound, although as previously mentioned, the advantage of cell electrolyte solution of the present invention is that it can tolerate the existence of water of these levels and non-excessive loss capability retention.
Above-mentioned ether-ether and mono alkyl ester compound are worked as and vinylene carbonate, 4-vinyl-1, when 3-dioxolanes-2-ketone and/or the combination of carbonic acid fluorinated ethylene ester, be good electrolyte solvent, and in described cell electrolyte solution, needn't comprise other electrolyte solvents.Especially, in described cell electrolyte solution, needn't comprise carbonate products (except carbonic acid fluorinated ethylene ester, when this compound exists), although can there be (if desired) in they.It is shocking, find, in cell electrolyte solution of the present invention, need there be carbonate products, the particularly non-halogenated alkylene ester of carbonic acid and the non-halogenated dialkyl of carbonic acid, and especially, the battery that contains described electrolyte solution is even also form stable SEI layer and functional under the situation that does not have these carbonate products.Therefore, in some embodiments, cell electrolyte solution contains and is no more than 20%, is no more than 10%, is no more than 5%, is no more than 2%, is no more than 1% or be no more than for example non-halogenated dialkyl of ethylene carbonate, propene carbonate and/or carbonic acid of 0.5% the non-halogenated alkylene ester of carbonic acid, and even can not contain these compounds.
They in addition, can have other solvents, as long as can be dissolved in ether ester compound or the mono alkyl ester with existing ratio.The example of these other solvents comprises for example alkyl ether, comprises dimethoxy-ethane, diethoxyethane, diethyl ether, oxolane etc.; Cyclic ethers class, for example gamma-butyrolacton, gamma-valerolactone, δ-Wu Neizhi etc.; Mononitriles, for example acetonitrile and propionitrile; Two nitriles are glutaronitrile for example; Symmetric sulfones class, for example dimethyl sulfone, diethyl sulfone etc.; Asymmetric sulfone class is ethyl-methyl sulfone, propyl group methyl sulfone etc. for example; Symmetry like this or the derivative of asymmetric sulfone class, for example methyl methoxy base ethyl sulfone, ethyl methoxy ethyl sulfone etc.; Cyclic sulfones (sulfolanes), for example sulfolane; Etc..Preferably, any other such solvents add up to be no more than described electrolyte solution total weight 30%, preferably be no more than 20%, more preferably no more than 10%, more preferably no more than 5% even more preferably no more than 1%, be most preferably not exceeding 0.5%.Described electrolyte solution can not contain other such solvents.
Under some situation of the present invention, cell electrolyte solution contains vinylene carbonate, 4-vinyl-1,3-dioxolanes-2-ketone, carbonic acid fluorinated ethylene ester or two or more the mixture in them.Vinylene carbonate, 4-vinyl-1,3-dioxolanes-2-ketone and/or carbonic acid fluorinated ethylene ester should account for its combined wt add ether ester compound and/or mono alkyl ester weight 0.5 to 20%.Can use bigger amount in principle, almost not have advantage but do like this.It is invalid to tend at the good battery aspect of performance of generation less than the amount of about 0.5 weight %.Preferred levels is weight 1% at least.Be limited to 5 weight % on preferred, be limited to 2.5 weight % on preferred, because in general this tittle is enough to obtain the ratio of good battery performance, particularly electrolyte volume (unit is microlitre) and battery capacity (unit is MAH) greater than in 10 the smaller batteries.The ratio of electrolyte volume (unit is microlitre) and battery capacity (unit is MAH) less than 10 than macrocell in, preferred 2wt.%, the more preferably 5wt.% at least of being limited to down at least is limited to 20wt.%, more preferably 15wt.%, more preferably 12wt.% on preferably.
Except already mentioned component, can there be various other additives in the cell electrolyte solution.These additives can comprise for example various cathodic protection agent, lithium salts stabilizer, lithium deposition improver, ionic solvation reinforcing agent, corrosion inhibitor, wetting agent, fire retardant (or thermal runaway inhibitor) and viscosity reducers.The additive of many these types is described in " A review on electrolyte additives for lithium-ion batteries " by Zhang, among J.Power Sources 162 (2006) 1379-1394.
The cathodic protection agent that is fit to comprises such as N N-diethylamino-trimethyl silane and LiB (C 2O 4) 2Material.The lithium salts stabilizer comprises LiF, three (2,2,2-trifluoroethyl) phosphite, 1-Methyl-2-Pyrrolidone, fluoro carbamate and hexamethyl phosphoramide.The example of lithium deposition improver comprises sulfur dioxide, polysulfide, carbon dioxide, surfactant such as tetra-alkyl ammonium chloride, PFOS lithium and tetraethyl ammonium salt, various PFPE etc.Crown ether can be the ionic solvation reinforcing agent that is fit to, and various boric acid, boron and borol (borole) compound also is like this.LiB (C 2O 4) 2And LiF 2C 2O 4It is the example of aluminium corrosion inhibitor.Cyclohexane, trialkylphosphate and some carboxylate can be used as wetting agent and viscosity reducers.The example of fire retardant or " thermal runaway inhibitor " comprises various phosphine oxide (O:PR 3), phosphinate (P (OR) R 2), phosphinate (P (OR 2) R), phosphite ester (P (OR) 3), phosphinate (O:P (OR) R 2), phosphonate ester (O:P (OR) 2R) and phosphate (O:P (OR) 3) tricresyl phosphate (2,2,2-trifluoroethyl) ester compounds for example, wherein each R is hydrogen or the alkyl with maximum 12 carbon atoms independently, and phosphonitrile (N=PR 2-) xCompound, wherein each R be halogen independently, have maximum 12 carbon atoms alkyl, have the alkyl amino of maximum 12 carbon atoms or have the alkyl oxygen base of maximum 12 carbon atoms, x is 3,4 or 5, and by the represented aromatics phosphorus compound of structure I:
Figure BPA00001735175400171
Wherein A is the group that contains one or more aromatic rings; Each R is alkylidene two bases that contain the aromatic ring carbon atom bonding of 1,2 or 3 carbon atom and direct and A group independently; Each R 1Be hydrogen, halogen, OH independently, have the alkyl of maximum 12 carbon atoms or have the alkoxyl of maximum 12 carbon atoms, two R that perhaps are connected with phosphorus atoms 1Group can lump together and form the ring structure that comprises described phosphorus atoms; And x is at least 1, is preferably 2 or 3.
Various other additives except fire retardant/thermal runaway inhibitor lump together and can account for maximum 20%, preferred maximum 10% of cell electrolyte solution total weight.Fire retardant/thermal runaway inhibitor can account for maximum 80 weight % of cell electrolyte solution.
Cell electrolyte solution is non-aqueous, this means that it contains the water that is no more than 0.5 weight %.The water of the cell electrolyte solution that obtains and pure content should be low as far as possible.The merging content of water and alcohols is 2000ppm or lower or 1000ppm or lower, is desired.The invention has the advantages that the battery that contains cell electrolyte solution of the present invention can tolerate such water and alcohols level, and does not significantly lose capability retention.The merging content of preferred water and alcohols is 100ppm or lower, 50ppm or lower or even 30ppm or lower.Various components are can be before forming electrolyte solution dry or handle separately, and/or can be with the electrolyte solution for preparing dry or otherwise handle to remove residual water and/or alcohols.The various components of electrolyte solution should not degraded or decompose to selected drying or processing method, also do not promote any reaction of not expecting between them.Can use by the use of thermal means, also can use for example molecular sieve of drier.
Cell electrolyte solution can or disperse described lithium salts, vinylene carbonate, 4-vinyl-1 by dissolving, and 3-dioxolanes-2-ketone or carbonic acid fluorinated ethylene ester and can be used for any other additive in the described ester compounds prepare easily.In general the order of mixing is not crucial.
Battery can be the battery of any kind, for example sodium ion, lithium ion, lithium sulphur, lithium metal, lithium polymer battery or lithium-air battery.
The battery that contains cell electrolyte solution of the present invention can have any available structure.Typical battery structure comprises anode and negative electrode, is inserted with dividing plate and described electrolyte solution between described anode and negative electrode, makes ion to move between anode and negative electrode by electrolyte solution.Assembly generally is packaged in the shell.To the shape of battery without limits.Battery can be to contain the battery that spiral twines the cylinder type of pellet electrode and dividing plate.Battery can be the battery of cylinder type of the structure of inside-out (inside-out) with the combination that comprises pellet electrode and dividing plate.Battery can be the battery that contains the flat type of overlapping electrode and dividing plate.
The anode material that is fit to for example comprises carbonaceous material for example phase microballoon, furnace black, acetylene black and various other graphitized material in the middle of natural or Delanium, carbonization pitch, carbon fiber, the graphitization.Carbonaceous material can use adhesive, and for example Kynoar, polytetrafluoroethylene, Styrene-Butadiene, isoprene rubber, polyvinyl acetate, polyethyl methacrylate, polyethylene or celluloid are bonded together.The carbon anodes that is fit to and building method thereof for example are described in the U.S. Patent number 7,169,511.
Other anode materials that are fit to comprise for example lithium titanate and metal oxide TiO for example of lithium metal, lithium alloy, other lithium compounds 2, SnO 2And SiO 2
The cathode material that is fit to comprises transition metal oxide, transition metal/lithium composite xoide, lithium/transition metal composite phosphate, transient metal sulfide, metal oxide, transition metal silicate, sulphur, polysulfide and air.The example of transition metal oxide comprises MnO, V 2O 5, V 6O 13And TiO 2Transition metal/lithium composite xoide comprises that basic composition is near LiCoO 2Lithium/cobalt composite oxide, basic composition near LiNiO 2Lithium/ni compound oxide and basic composition near LiMn 2O 4Or LiMnO 2Lithium/manganese composite oxide.Under every kind of these situation, a part of lithium, cobalt, nickel or manganese can for example Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Mg, Ga or Zr replace by one or both metals.Wherein a part of lithium, cobalt, nickel or manganese by one or both metals transition metal/lithium composite xoide of replacing of Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mg, Ga or Zr for example, also comprise having formula Li X+yM zMn 2-y-zO 4Lithium insert compound, wherein said insertion compound has spinelle sample crystal structure, M is for example Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mg, Ga or Zr of metal, x is more than or equal to 0 and less than 1 number, y is more than or equal to 0 and less than 0.33 number, z is greater than 0 and less than about 1 number, and lithium inserts the electromotive force of compound with respect to Li/Li +Be higher than about 4.5 volts.Lithium/transition metal composite phosphate comprises iron lithium phosphate, lithium phosphate manganese, lithium phosphate cobalt, lithium phosphate ferrimanganic etc., and described in for example WO 2009/127901 and WO 2009/144600.The example of available metal silicate comprises lithium orthosilicate iron.
Electrode generally electrically contacts with current-collector separately or is formed on the current-collector.The current-collector that is applicable to anode is for example copper, copper alloy, nickel, nickel alloy, stainless steel, titanium etc. of metal or metal alloy.The current-collector that is applicable to negative electrode comprises aluminium, titanium, tantalum, two or more the alloy etc. in them.
Dividing plate is inserted between anode and the negative electrode, to prevent that anode and negative electrode from coming in contact each other and short circuit.Dividing plate is non-conducting material aptly.It should or not be dissolved in wherein with any component reaction of electrolyte solution or electrolyte solution under service conditions.In general, polymeric separator plates is fit to.The example that is applicable to the polymer that forms dividing plate comprises polyethylene, polypropylene, poly-1-butylene, poly-3-methylpentene, ethylene-propylene copolymer, polytetrafluoroethylene, polystyrene, polymethyl methacrylate, dimethyl silicone polymer, polyether sulfone etc.
Electrolyte solution must can see through dividing plate.Therefore, dividing plate generally is porose, takes the form of porous plate, non-woven or Woven fabric etc.The porosity of dividing plate is generally 20% or higher, reaches as high as 90%.Preferred porosity is 30 to 75%.The longest dimension in hole generally is not more than 0.5 micron, preferred maximum 0.05 micron.Block board thickness is generally at least 1 micron, and can be up to 50 microns.Preferred thickness is 5 to 30 microns.
Battery is preferably secondary (chargeable) battery, more preferably serondary lithium battery.In such battery, exoelectrical reaction comprises lithium ion from anodic solution or takes off lithium to electrolyte solution and lithium ion is incorporated in the negative electrode simultaneously.On the contrary, the charging reaction comprises that lithium ion is incorporated into the anode from electrolyte solution.After charging, lithium ion is reduced in anode-side, and the lithium ion in the cathode material is dissolved in the electrolyte solution simultaneously.
Battery of the present invention can be used in for example electric motor car of commercial Application, hybrid-power electric vehicle, plug-in hybrid-power electric vehicle, spacecraft and equipment, the electric bicycle etc.Battery of the present invention also can be used for moving a large amount of Electrical and Electronic devices, for example for example pacemaker and defibrillator of computer, camera, video camera, cell phone, PDA, MP3 and other music players, instrument, television set, toy, video game machine, household electrical appliance, medical treatment device, and many other devices.
Provide the following examples with explanation the present invention, but do not planned to limit the scope of the invention.Unless otherwise, otherwise all umbers and percentage by weight.
Embodiment 1-2 and control cell A and B
Will be by LiPF 6The control cell electrolyte solution that 1.0M solution in the mixture of the ethylene carbonate of by volume 50/50 and diethyl carbonate constitutes is introduced and is had high power Li 1.1(Ni 1/3Mn 1/3Co 1/3) 0.9O 2(NMC) in 2025 button cells of negative electrode, graphite anode and polyolefin separator.Described button cell is named as control cell A.The bulk density of electrolyte solution is 1.3g/mL down at 25 ℃.Use Maccor 4000 cell testers, (after SEI forms circulation) uses the discharge rate of 0.5C, 0.1C, 0.33C, 1C, 2C, 3C, 5C, 8C, 10C, 12C, 15C, 20C and last 0.1C successively, produces the discharge curve of circulation fully of control cell A.Representative discharge curve from this test is shown as curve " A " in Fig. 1.
Prepared second identical battery (also being named as control cell A).Using the same test instrument to carry out the discharge curve that this battery was tested and produced to cycle performance, wherein at first use initial 0.1C discharge rate, is the repeat pattern that 25 1C discharge cycles are right after another 0.1C discharge cycles, until carrying out 100 discharge cycles then.The representative discharge curve that comes from this cycle performance test is designated as curve " A " in Fig. 2.
Prepare control cell B with the same manner, difference is that electrolyte solution is LiPF 61.0M solution in the ethylene carbonate of 98 parts of by volumes 50/50 and diethyl carbonate mixture and 2 parts of vinylene carbonates.Carry out the cycle performance test in the mode identical with being used for control cell A.The representative discharge curve that comes from this cycle performance test is designated as curve " B " in Fig. 2.
Make battery embodiment 1 with the same manner, difference is that electrolyte solution is by LiPF 61.0M solution in the vinylene carbonate of the acetic acid methoxy ethyl ester of 98 weight % and 2 weight % constitutes.In the mode identical with control cell A at battery embodiment 1 discharge test that circulates fully.The representative discharge curve that comes from this discharge test that circulates fully is designated as curve 1 in Fig. 1.Carry out the cycle performance test in the mode identical with B with being used for control cell A.The representative discharge curve that comes from the cycle performance test is designated as curve 1 in Fig. 1.
Make battery embodiment 2 with the same manner, difference is that electrolyte solution is by LiPF 698% acetic acid ethoxyethyl group ester by weight and by weight the 1.0M solution in 2% the vinylene carbonate constitute.In the mode identical with control cell A at battery embodiment 2 discharge test that circulates fully.The representative discharge curve that comes from the discharge test that circulates fully is designated as curve 2 in Fig. 1.
As shown in fig. 1, on the discharge test that circulates fully, battery embodiment 1 (contain acetic acid methoxy ethyl ester and add that 2% vinylene carbonate is as solvent) compares performance quite with control cell A or better.Be lower than under the 3C discharge rate, the specific capacity of battery embodiment 1 comparison is higher than battery A, and at all more under the high rate discharge, approaches very much or equals control cell A.This result is very amazing, because the ethylene carbonate of control cell A/diethyl carbonate solvent mixture has represented the prior art state in lithium battery field, and since different with component among the control cell A, and do not know that acetic acid methoxy ethyl ester forms the SEI layer.At 5C and more under the low discharge rate, the performance of battery embodiment 2 and battery embodiment 1 are closely similar.
Fig. 2 shows that in the cycle performance test, battery embodiment 1 keeps its specific capacity better than any control cell.In this test, compare with battery embodiment 1, in early stage (before the 20th circulation) of cycle performance test, control cell A shows higher slightly specific capacity, but its specific capacity reduces sooner.After about 50 circulations, the specific capacity of battery embodiment 1 surpasses control cell A.The from the 38th to the 100th circulation, the specific capacity of battery embodiment 1 only loses 0.49%, and the capacity of control cell A loses 2.86% in the meantime.In this test, battery embodiment 1 is shown in has the comparison probable life longer than battery A under the equal or better specific capacity.
The result of control cell B has shown the influence of adding 2% vinylene carbonate in ethylene carbonate/diethyl carbonate dicyandiamide solution.Both are lower than battery A and battery embodiment 1 for specific capacity comparison, and the capacitance loss rate is obviously higher.The result who comes from control cell B shows, adds vinylene carbonate and in fact damage battery performance in ethylene carbonate/diethyl carbonate dicyandiamide solution, although vinylene carbonate is considered to play the effect that SEI forms additive.
Embodiment 3
Prepare battery embodiment 3A-3E in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of acetic acid methoxy ethyl ester and vinylene carbonate.The acetic acid methoxy ethyl ester of these embodiment and the ratio of vinylene carbonate are as follows:
Embodiment 3A:99.5% acetic acid methoxy ethyl ester and 0.5% vinylene carbonate;
Embodiment 3B:99% acetic acid methoxy ethyl ester and 1% vinylene carbonate;
Embodiment 3C:98% acetic acid methoxy ethyl ester and 2% vinylene carbonate;
Embodiment 3D:95% acetic acid methoxy ethyl ester and 5% vinylene carbonate;
Embodiment 3E:90% acetic acid methoxy ethyl ester and 10% vinylene carbonate.
In as hereinbefore mode to each battery embodiment 3A-3E discharge cycles that circulates fully.The representative discharge curve that comes from the discharge test that circulates fully of each these battery is denoted as curve 3A-3E respectively in Fig. 3.
Manufacturing is with battery like control cell A and the category-B and test to be used for reference.The representative discharge curve that comes from the discharge test that circulates fully of each these control cell is denoted as curve A and B in Fig. 3.
Curve 3A-3E has indicated the influence of adding vinylene carbonate in the acetic acid methoxy ethyl ester cell electrolyte solution.Add relatively large vinylene carbonate and cause in whole test loop, producing much higher battery capacity.This result is opposite with the result that when adding vinylene carbonate to ethylene carbonate/diethyl carbonate solution (in control cell B) obtains, and not observing discharge capacity under latter event increases.As shown in Figure 3, add 1% vinylene carbonate to acetic acid methoxy ethyl ester electrolyte solution and compare the raising that produces highly significant with the situation of 0.5% vinylene carbonate.Vinylene carbonate further is doubled to 2%, causes the raising of other highly significant.Vinylene carbonate content further is increased to 10%, in this test, provides less specific capacity to improve.But battery that do not contain carbonic acid vinylene similar to embodiment 3A-3E can not charge, and shows and do not have specific capacity basically.
Embodiment 4
Prepare battery embodiment 4 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At acetic acid 2-methoxyl group-1-Methylethyl ester of 98% by weight and the 1.0M solution in the mixture of 2% vinylene carbonate by weight.Acetic acid 2-methoxyl group-1-Methylethyl ester is commercially available material Dowanol TMPMA, it has been distilled so that water and residual alcohols content are reduced to separately and has been lower than 50ppm.This material has-87 ℃ solidifying point, than the high 10 ℃ flash-point of ethylene carbonate, and the bulk density of 0.97g/mL only, the density of ethylene carbonate is 1.321g/mL in contrast to this.The bulk density of described electrolyte solution only is 1.1g/mL.Produce the discharge curve of circulation fully of battery embodiment 4 and control cell A as previously mentioned, representative curve is named as " 4 " and " A " respectively in Fig. 4.
As shown in Figure 4,1: 1 mixture with acetic acid 2-methoxyl group-1-Methylethyl ester (containing 2% vinylene carbonate) replacement ethylene carbonate and diethyl carbonate has produced the battery with comparable performance.
Embodiment 5-9 and control cell C-J
Prepare battery embodiment 5 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% acetic acid methoxy ethyl ester by weight and the 1.0M solution in the mixture of 5% vinylene carbonate by weight.
Prepare battery embodiment 6 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% acetic acid methoxy ethyl ester and 5% 4-vinyl-1 by weight by weight, the 1.0M solution in the mixture of 3-dioxolanes-2-ketone.
Prepare control cell C in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% acetic acid methoxy ethyl ester by weight and the 1.0M solution in the mixture of 5% vinyl acetate by weight.
Prepare control cell D in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% acetic acid methoxy ethyl ester by weight and the 1.0M solution in the mixture of 5% carbonic acid allyl methyl ester by weight.
Prepare control cell E in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% acetic acid methoxy ethyl ester by weight and the 1.0M solution in the mixture of 5% benzene sulfonic acid alkynes propyl ester by weight.
Prepare control cell F in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% acetic acid methoxy ethyl ester by weight and the 1.0M solution in the mixture of 5% methyl chlorocarbonate by weight.
Obtain battery embodiment 5 and 6 and the discharge curve of circulation fully of control cell A, C, D and E as mentioned above.Representative curve is shown as curve 5,6, A, C, D and E respectively in Fig. 5.Control cell F does not possess electric charge under 4.2 volts, do not test.
Presentation of results shown in Fig. 5 in the electrolyte solution based on ester, how important the selection of SEI additive has to performance.Vinylene carbonate and 4-vinyl-1,3-dioxolanes-2-ketone performance is very good, contains their performance of battery with to represent the control cell A of prior art state suitable in electrolyte solution.Remaining SEI additive does not produce good battery performance, although except methyl chlorocarbonate all with vinylene carbonate and 4-vinyl-1,3-dioxolanes-2-ketone equally is the polymerizable type.These results show, the performance of SEI additive in acetic acid methoxy ethyl ester electrolyte solution be not easy to predict, and are not understood well with the mechanism that the dicyandiamide solution based on ester produces good battery performance.
Form control cell G-J in the mode identical with control cell A, difference is that electrolyte solution in each case is LiPF 61.0M solution in following solvent mixture:
Control cell G: 90/10 acetic acid methoxy ethyl ester and the mixture of ethylene carbonate by weight;
Control cell H: 95/5 acetic acid methoxy ethyl ester and the mixture of ethylene carbonate by weight;
Control cell I: 98/2 acetic acid methoxy ethyl ester and the mixture of ethylene carbonate by weight;
Control cell J: 99/1 acetic acid methoxy ethyl ester and the mixture of ethylene carbonate by weight.
Obtain the discharge curve of circulation fully of control cell G-J as mentioned above.Representative curve is shown as curve G, H, I and J respectively in Fig. 6.Also show the representative discharge curve of control cell A.
Result shown in the table 6 shows, and is opposite with the suggestion in U.S. publication application 2008-0241699, seems that performance is bad when ethylene carbonate itself forms agent as SEI when the ester solvent system is added on a small quantity.The low specific capacity that bad SEI forms by control cell G-J is confirmed.
Form battery embodiment 7-9 in the mode identical with control cell A, difference is that electrolyte solution is LiPF in each case 61.0M solution in following solvent mixture:
Battery embodiment 7: 50/50 acetic acid methoxy ethyl ester and the mixture of ethylene carbonate mix with 2 parts of vinylene carbonates by weight with 100 parts.
Battery embodiment 8: 75/25 acetic acid methoxy ethyl ester and the mixture of ethylene carbonate mix with 2 parts of vinylene carbonates by weight with 100.
Battery embodiment 9: 50/50 ethylene carbonate and the mixture of diethyl carbonate mix with 10 parts of acetic acid methoxy ethyl esters and 2 parts of vinylene carbonates by weight with 100 parts.
Obtain the discharge curve of circulation fully of battery embodiment 7-9 as mentioned above.Representative curve is shown as curve 7,8 and 9 respectively in Fig. 7.Also show the representative discharge curve of control cell A.
Result shown in the table 7 shows, carbonate solvent for example ethylene carbonate and ester class for example the mixture of acetic acid methoxy ethyl ester can be formed with the cell electrolyte solvent of usefulness, if also exist SEI to form for example vinylene carbonate of agent.Yet the performance of battery embodiment 7-9 is be not as good as embodiments of the invention 1,2,3C, 4 or 5 performance, shows that to comprise the plutonium carbonate alkylene ester not too preferred.
Embodiment 10-12 and control cell K-O
Prepare battery embodiment 10 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% Dowanol by weight TM1.0M solution in the mixture of PMA acetic acid 2-methoxyl group-1-Methylethyl ester and 5% vinylene carbonate by weight, described Dowanol TMPMA acetic acid 2-methoxyl group-1-Methylethyl ester has been distilled so that water and residual alcohols content are reduced to separately and has been lower than 50ppm.
Prepare battery embodiment 11 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% distilled Dowanol by weight TMPMA and 5% 4-vinyl-1 by weight, the 1.0M solution in the mixture of 3-dioxolanes-2-ketone.
Prepare battery embodiment 12 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% distilled Dowanol by weight TM1.0M solution in the mixture of PMA and 5% carbonic acid fluorinated ethylene ester by weight.
Prepare control cell K in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% distilled Dowanol by weight TMPMA with by weight 5% 1, the 1.0M solution in the mixture of 3-N-morpholinopropanesulfonic acid lactone.
Prepare control cell L in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% distilled Dowanol by weight TM1.0M solution in the mixture of PMA and 5% benzene sulfonic acid alkynes propyl ester by weight.
Prepare control cell M in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% distilled Dowanol by weight TM1.0M solution in the mixture of PMA and 5% carbonic acid allyl methyl ester by weight.
Prepare control cell N in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 98% distilled Dowanol by weight TMPMA with by weight 2% 1, the 1.0M solution in the mixture of 3-N-morpholinopropanesulfonic acid lactone.
Prepare control cell O in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 6At 95% distilled Dowanol by weight TM1.0M solution in the mixture of PMA and 5% vinyl acetate by weight.
Obtain the discharge curve of circulation fully of battery embodiment 10-12 and control cell A and K-O as previously mentioned.Representative curve is shown as curve 10,11,12, A, K, L, M, N and O respectively in Fig. 8.
Presentation of results shown in Fig. 8 in based on the electrolyte solution of acetic acid 2-methoxyl group-1-Methylethyl ester the selection of SEI additive performance is had how important.Vinylene carbonate, 4-vinyl-1,3-dioxolanes-2-ketone and carbonic acid fluorinated ethylene ester performance are very good, contain their performance of battery with to represent the control cell A of prior art state suitable in electrolyte solution.Remaining SEI additive does not produce good battery performance.These results show, the performance of SEI additive in acetic acid 2-methoxyl group-1-Methylethyl ester electrolyte solution be not easy to predict, and are not understood well with the mechanism that this dicyandiamide solution produces good battery performance.
Control cell P1, P2 and P3
Prepare control cell P1 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 75/25 and isobutyryl methyl acetate and 2 parts of vinylene carbonates.
Prepare control cell P2 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 50/50 and isobutyryl methyl acetate and 2 parts of vinylene carbonates.
Prepare control cell P3 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 25/75 and isobutyryl methyl acetate and 2 parts of vinylene carbonates.
Obtain the discharge curve of circulation fully of control cell A and P1-P3 as previously mentioned.Representative curve is shown as curve A, P1, P2 and P3 respectively in Fig. 9.
These results show that the isobutyryl methyl acetate reduces battery performance strongly, even when uniting use with cells known electrolyte solvent (ethoxyl methyl ethyl sulfone) and vinylene carbonate, and have emphasized the unpredictability of candidate's solvent nature.
Embodiment 13-15 and control cell Q1 and Q2
Prepare battery embodiment 13 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 25/75 and acetic acid 2-ethoxyethyl group ester and 2 parts of vinylene carbonates.
Prepare battery embodiment 14 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 50/50 and acetic acid 2-ethoxyethyl group ester and 2 parts of vinylene carbonates.
Prepare battery embodiment 15 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 75/25 and acetic acid 2-ethoxyethyl group ester and 2 parts of vinylene carbonates.
Prepare control cell Q1 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 25/75 and diethy-aceto oxalate and 2 parts of vinylene carbonates.
Prepare control cell Q2 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 50/50 and diethy-aceto oxalate and 2 parts of vinylene carbonates.
Obtain the discharge curve of circulation fully of battery embodiment 13-15 and control cell A and Q1 and Q2 as previously mentioned.Representative curve is shown as curve 13,14,15, A, Q1 and Q2 respectively in Figure 10.
These results show that diethy-aceto oxalate reduces battery performance strongly, even when uniting use with cells known electrolyte solvent (ethoxyl methyl ethyl sulfone) and vinylene carbonate.Work was good when on the other hand, acetic acid 2-ethoxyethyl group ester and ethoxyl methyl ethyl sulfone and vinylene carbonate made up.
Control cell R1, R2 and R3
Prepare control cell R1 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 75/25 and gamma-valerolactone and 2 parts of vinylene carbonates.
Prepare control cell R2 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 50/50 and gamma-valerolactone and 2 parts of vinylene carbonates.
Prepare control cell R3 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in the mixture of the ethoxyl methyl ethyl sulfone of 98 parts of by volumes 25/75 and gamma-valerolactone and 2 parts of vinylene carbonates.
Obtain the discharge curve of circulation fully of control cell A and R1-R3 as previously mentioned.Representative curve is shown as curve A, R1, R2 and R3 respectively in Figure 11.
These results show that gamma-valerolactone reduces battery performance, even when uniting use with cells known electrolyte solvent (ethoxyl methyl ethyl sulfone) and vinylene carbonate.These results emphasize the unpredictability of candidate's solvent nature again.
Embodiment 16-17 and control cell S
Prepare battery embodiment 16 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in 98 parts of butyl acetates and 2 parts of vinylene carbonates.
Prepare battery embodiment 17 in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in 98 parts of hexyl acetates and 2 parts of vinylene carbonates.
Prepare control cell S in the general mode identical with control cell A, difference is that electrolyte solution is LiPF 61.0M solution in 98 parts of octyl acetates and 2 parts of vinylene carbonates.
Obtain battery embodiment 16 and 17 and the discharge curve of circulation fully of control cell A and S as previously mentioned.Representative curve is shown as curve 16,17, A and S respectively in Figure 12.
These results show that the electrolyte solution based on ethylene carbonate/diethyl carbonate of the performance that butyl acetate combines with vinylene carbonate and prior art state is suitable.The performance that hexyl acetate combines with vinylene carbonate is weaker slightly.Yet the performance of octyl acetate is very different, even when having vinylene carbonate.
Embodiment 18-22 and comparative sample T
Will be by LiPF 6The control cell electrolyte solution that 1.0M solution in the mixture of the ethylene carbonate of by volume 50/50 and diethyl carbonate constitutes is incorporated into 18650 spirals and twines in the battery.Described battery is named as control cell T.This battery contains 4000 microlitre cell electrolyte solutions and has the capacity of 2000mAh.
Make battery embodiment 18 in the same manner, difference is that electrolyte solution is by LiPF 698% acetic acid methoxy ethyl ester by weight and by weight the 1.0M solution in the mixture of 2% vinylene carbonate constitute.The performance of battery embodiment 18 is not so good as control cell T, and demonstration discharges some gases in cycle period.
Make battery embodiment 19 in the same manner, difference is that electrolyte solution is by LiPF 6At 98% anhydrous Dowanol by weight TM1.0M solution in the mixture of the vinylene carbonate of PMA and 2 weight % constitutes.The performance of battery embodiment 19 and battery embodiment 18 are similar.
Make battery embodiment 20 in the same manner, difference is that electrolyte solution is by LiPF 698 weight % with 4: 1 anhydrous Dowanol of by volume TMPMA: the 1.0M solution in the mixture of the vinylene carbonate of ethylene carbonate blend and 2 weight % constitutes.The performance of battery embodiment 20 is suitable with control cell T.
Make battery embodiment 21 in the same manner, difference is that electrolyte solution is by LiPF 6At 90% anhydrous Dowanol by weight TM1.0M solution in the mixture of the vinylene carbonate of PMA and 10 weight % constitutes.The performance of battery embodiment 21 and battery embodiment 18 are similar.This embodiment is with embodiment 19, confirmed ratio at electrolyte volume and capacity be about 2 than macrocell in, may need relatively large vinylene carbonate to form and freeze thaw stability to obtain good SEI.
Make battery embodiment 22 in the same manner, difference is that electrolyte solution is by LiPF 6At 98% anhydrous Dowanol by weight TMThe 4-vinyl-1 of PMA and 10 weight %, the 1.0M solution in the mixture of 3-dioxolanes-2-ketone constitutes.The performance of battery embodiment 22 and control cell T are similar, and show again and may need relatively large vinylene carbonate to form and freeze thaw stability to obtain good SEI in than macrocell.
Embodiment 23 and control cell U
Will be by LiPF 6The control cell electrolyte solution that 1.0M solution in the mixture of the ethylene carbonate of by volume 50/50 and diethyl carbonate constitutes is introduced and is had high power Li 1.1(Ni 1/3Mn 1/3Co 1/3) 0.9O 2(NMC) in 2025 button cells of negative electrode, graphite anode and polyolefin separator.The water content of this cell electrolyte solution is about 1000ppm.Described button cell is named as control cell U.
Make battery embodiment 23 in the same manner, difference is that electrolyte solution is by LiPF 61.0M solution in the mixture of the vinylene carbonate of 98% Dowanol PMA and 2 weight % by weight constitutes.The water content of this electrolyte solution also is about 1000ppm.
With identical among the embodiment of front, control cell U and battery embodiment 23 are carried out the cycle performance test.Control cell U is only losing about 12% capacity after 100 circulations.Battery embodiment 23 only loses about 3.5% capacity after 100 circulations.
Embodiment 24-27
In battery embodiment 24, use platinum work electrode, lithium paper tinsel that electrode and reference electrode are recorded by LiPF 6At acetic acid 2,2, cyclic voltammetric (the current density μ A/cm of the cell electrolyte solution that the 1.0M solution in the 2-trifluoroethyl ester constitutes 2To for Li/Li +Electromotive force V).Sweep speed is 50mV/s, and at 300 μ A/cm 2Current density under calculating voltage stability.The discovery voltage stability is 4.89V.
With with embodiment 24 in identical mode carry out battery embodiment 25, difference is that electrolyte solution is by LiPF 61.0M solution in 3,3,3-trifluoroacetic acid ethyl ester constitutes.The discovery voltage stability is 4.67V.
With with embodiment 24 in identical mode carry out battery embodiment 26, difference is that electrolyte solution is by LiPF 61.0M solution in the 2-methylfluoracetate constitutes.The discovery voltage stability is 4.79V.
With with embodiment 24 in identical mode carry out battery embodiment 27, difference is that electrolyte solution is by LiPF 61.0M solution in 2-methoxyacetic acid 2-methoxyl group-1-Methylethyl ester constitutes.The discovery voltage stability is 4.58V.

Claims (17)

1. non-aqueous batteries electrolyte solution, it comprises:
(1) at least a lithium salts, its amount provides the described lithium salt solution of 0.1M at least in described cell electrolyte solution,
(2) at least a have the ether ester compound of maximum 12 carbon atoms, at least a mono alkyl ester compound or its mixture with maximum 8 carbon atoms, described lithium salts solubilized therein arrives at least 0.1 mole every liter degree, wherein said ether ester compound or mono alkyl ester compound can partially or completely be fluoridized, and
(3) based on the combined wt of component (2) and (3), 0.5 to 20wt.% vinylene carbonate, 4-vinyl-1,3-dioxolanes-2-ketone, carbonic acid fluorinated ethylene ester or its any two or more kinds of mixtures.
2. the described cell electrolyte solution of claim 1, it contains other solvents of 0 to 30% by weight.
3. claim 1 or 2 described cell electrolyte solution, it contains 0 to 30% ethylene carbonate, propene carbonate, dialkyl carbonate or its mixture by weight.The adjusting of CTE is mainly according to other filler particles.The RFC fiber has the CTE near ACM, and biosoluble fibers has the CTE higher than ACM, and most of thin slice (for example, aluminium) also has the CTE higher than ACM.I know that in the latter half, you are discussing about auxiliary particle and are being used for accommodation property.This may be good strategy, because some reinforcement may reduce CTE independently.If not so, must add the ceramic particle of additional amount so.
4. the described cell electrolyte solution of claim 3, it contains and is no more than 5% ethylene carbonate, propene carbonate, dialkyl carbonate or its mixture by weight.
5. each described cell electrolyte solution of claim 1-4, wherein component (2) comprises at least a acetic acid 2-alkoxyethyl ester, acetic acid 2-alkoxyl-1-alkyl ethyl ester or acetic acid 2-alkoxyl-2-alkyl ethyl ester with maximum 12 carbon atoms.
6. the optional described cell electrolyte solution of claim 1-4, wherein component (2) is two or more mixture of acetic acid 2-methoxy ethyl ester, acetic acid 2-ethoxyethyl group ester, acetic acid 2-methoxyl group-1-Methylethyl ester, acetic acid 2-methoxyl group-2-Methylethyl ester, acetic acid 2-ethyoxyl-1-Methylethyl ester, acetic acid 2-ethyoxyl-2-Methylethyl ester or its.
7. each described cell electrolyte solution of claim 1-4, wherein component (2) is propionic acid 2-methoxy ethyl ester, propionic acid 2-ethoxyethyl group ester, propionic acid 2-methoxyl group-1-Methylethyl ester, propionic acid 2-ethyoxyl-1-Methylethyl ester, propionic acid 2-methoxyl group-2-Methylethyl ester, propionic acid 2-ethyoxyl-2-Methylethyl ester, acetic acid 2-methoxyl group-1-Methylethyl ester, acetic acid 2-ethyoxyl-1-Methylethyl ester, acetic acid 2-methoxyl group-2-Methylethyl ester, acetic acid 2-ethyoxyl-2-Methylethyl ester, acetic acid 2-methoxyl group-1-Methylethyl ester, acetic acid 2-ethyoxyl-1-Methylethyl ester, acetic acid 2-methoxyl group-2-Methylethyl ester, acetic acid 2-ethyoxyl-2-Methylethyl ester, or its any two or more mixture.
8. each described cell electrolyte solution of claim 1-4, wherein component 2 is any two or more the mixtures of methyl formate, Ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl valerate, ethyl valerate, ethyl isovalerate, ethyl hexanoate, methyl caproate or its.
9. non-aqueous batteries electrolyte solution, it comprises:
(1) at least a lithium salts, its amount provides the described lithium salt solution of 0.1M at least in described cell electrolyte solution, and
(2) have acetic acid 2-alkoxyl-1-alkyl ethyl ester or the acetic acid 2-alkoxyl-2-alkyl ethyl ester of maximum 12 carbon atoms, wherein said alkoxyl contains 1 to 7, preferred 1 to 3, more preferably 1 or 2 carbon atom and can be by fluoro partially or completely, and wherein said alkyl contains 1 to 7, preferred 1 to 3, more preferably 1 or 2 carbon atom and can be by fluoro partially or completely, and the amount of described ester is enough to dissolve described lithium salts.
10. the described cell electrolyte solution of claim 9, it also comprises (3) based on the combined wt of component (2) and (3), 0.5 to 10wt.% vinylene carbonate or 4-vinyl-1,3-dioxolanes-2-ketone.
11. the described cell electrolyte solution of claim 8 or 9, wherein said acetic acid 2-alkoxyl-1-alkyl ethyl ester or acetic acid 2-alkoxyl-2-alkyl ethyl ester compound are two or more mixtures of acetic acid 2-methoxy ethyl ester, acetic acid 2-ethoxyethyl group ester, acetic acid 2-methoxyl group-1-Methylethyl ester, acetic acid 2-methoxyl group-2-Methylethyl ester, acetic acid 2-ethyoxyl-1-Methylethyl ester, acetic acid 2-ethyoxyl-2-Methylethyl ester or its.
12. a non-aqueous batteries electrolyte solution, it comprises:
(1) at least a lithium salts, its amount provides the described lithium salt solution of 0.1M at least in described cell electrolyte solution, and
(2) by the ether ester compound of structure I and any expression of II, wherein structure I is
Figure FPA00001735175300031
R wherein 1Be hydrogen, have straight or branched alkyl or a R of 1 to 5 carbon atom 4-O-R 5-group, wherein R 4Be alkyl, R 5Be alkylidene, and R 4And R 5Lump together and have maximum 5 carbon atoms, R 2Be the straight or branched alkylidene with 1 to 7 carbon atom, R 3Be the branched-chain or straight-chain alkyl with 1 to 3 carbon atom, wherein R 1, R 2And R 3Lump together and have maximum 12 carbon atoms, and R 1, R 2And R 3In at least one fluoridized by at least part of,
Structure I I is
Figure FPA00001735175300041
R wherein 6Be hydrogen, have straight or branched alkyl or a R of 1 to 6 carbon atom 8-O-R 9-group, wherein R 8Be alkyl, R 9Be alkylidene, and R 8And R 9Lump together and have maximum 6 carbon atoms, R 7Be the straight or branched alkyl with maximum 6 carbon atoms, wherein R 6And R 7In at least one fluoridized and R wherein by at least part of 6And R 7Lump together and have maximum 7 carbon atoms.The present invention still is a kind of battery, and described battery comprises the dividing plate between anode, negative electrode, insertion anode and the negative electrode, and this cell electrolyte solution contacts with negative electrode with anode.
13. each described cell electrolyte solution of claim 1-12, wherein said lithium salts is LiPF 6, LiClO 4, LiBF 4, LiAsF 6, LiCF 3SO 3And Li[(CF 3SO 3) 2N] at least a.
14. each described cell electrolyte solution of claim 1-13, it also comprises at least a other additives that are selected from cathodic protection agent, lithium salts stabilizer, lithium deposition improver, ionic solvation reinforcing agent, corrosion inhibitor, wetting agent and the viscosity reducers.
15. a battery, it comprises anode, negative electrode, be configured between described anode and the negative electrode dividing plate and with described anode and the contacted electrolyte solution of negative electrode, wherein said electrolyte solution is each cell electrolyte solution of claim 1-14.
16. the described battery of claim 15, it is secondary cell.
17. the described battery of claim 15 or 16, it is lithium ion, lithium sulphur, lithium metal or lithium polymer battery.
CN201180060551.1A 2010-12-15 2011-12-13 Containing some based on the cell electrolyte solution of the solvent of ester and the battery containing such electrolyte solution Expired - Fee Related CN103262329B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US42314710P 2010-12-15 2010-12-15
US61/423,147 2010-12-15
PCT/US2011/064681 WO2012082760A1 (en) 2010-12-15 2011-12-13 Battery electrolyte solution containing certain ester-based solvents, and batteries containing such an electrolyte solution

Publications (2)

Publication Number Publication Date
CN103262329A true CN103262329A (en) 2013-08-21
CN103262329B CN103262329B (en) 2016-02-10

Family

ID=45470700

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180060551.1A Expired - Fee Related CN103262329B (en) 2010-12-15 2011-12-13 Containing some based on the cell electrolyte solution of the solvent of ester and the battery containing such electrolyte solution

Country Status (7)

Country Link
US (1) US9472813B2 (en)
EP (1) EP2652832A1 (en)
JP (1) JP5886870B2 (en)
KR (1) KR20130130775A (en)
CN (1) CN103262329B (en)
CA (1) CA2821958A1 (en)
WO (1) WO2012082760A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105762410A (en) * 2016-04-01 2016-07-13 宁德新能源科技有限公司 Non-aqueous electrolyte and lithium-ion battery using same
CN106207262A (en) * 2015-05-25 2016-12-07 松下知识产权经营株式会社 Electrolyte and battery
CN110534807A (en) * 2019-09-29 2019-12-03 河南省法恩莱特新能源科技有限公司 A kind of LiNi0.5Mn1.5O4Positive lithium-ion battery electrolytes and preparation method
CN110611084A (en) * 2018-06-15 2019-12-24 武汉大学 Lithium-sulfur secondary battery with long cycle life and 100% coulombic efficiency
CN111656595A (en) * 2018-01-30 2020-09-11 大金工业株式会社 Electrolyte solution, electrochemical device, lithium ion secondary battery, and assembly
CN111758180A (en) * 2017-10-31 2020-10-09 关东电化工业株式会社 Nonaqueous electrolyte solution and nonaqueous electrolyte battery
WO2023179456A1 (en) * 2022-03-25 2023-09-28 深圳新宙邦科技股份有限公司 Non-aqueous electrolyte and secondary battery

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2720307B1 (en) * 2011-06-08 2020-04-01 LG Chem, Ltd. Non-aqueous electrolyte and lithium secondary battery using the same
CN103688402B (en) * 2011-07-14 2016-05-11 株式会社Lg化学 Non-aqueous electrolytic solution and the lithium secondary battery that uses it
US20140227611A1 (en) * 2011-09-20 2014-08-14 Nec Corporation Non-Aqueous Secondary Battery
JP2014078433A (en) * 2012-10-11 2014-05-01 Fujifilm Corp Electrolytic solution for nonaqueous secondary battery use, and nonaqueous electrolyte secondary battery
JP5923747B2 (en) 2013-12-04 2016-05-25 パナソニックＩｐマネジメント株式会社 Sodium secondary battery
US10263283B2 (en) * 2014-01-30 2019-04-16 Wildcat Discovery Technologies, Inc Electrolyte formulations
JP7272745B2 (en) * 2014-07-14 2023-05-12 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー COMPOSITION FOR SUPPRESSING COMBUSTION IN LITHIUM-ION BATTERY
US9755235B2 (en) 2014-07-17 2017-09-05 Ada Technologies, Inc. Extreme long life, high energy density batteries and method of making and using the same
KR102343690B1 (en) 2014-12-31 2021-12-29 삼성전자주식회사 Electrolyte solution for lithium secondary battery and lithium secondary battery employing the same
WO2016160703A1 (en) 2015-03-27 2016-10-06 Harrup Mason K All-inorganic solvents for electrolytes
WO2016209460A2 (en) * 2015-05-21 2016-12-29 Ada Technologies, Inc. High energy density hybrid pseudocapacitors and method of making and using the same
US9887434B2 (en) 2015-06-22 2018-02-06 Wildcat Discovery Technologies, Inc Electrolyte formulations for lithium ion batteries
US9466857B1 (en) 2015-06-22 2016-10-11 Wildcat Discovery Technologies, Inc. Electrolyte formulations for lithium ion batteries
US10547083B2 (en) 2015-06-22 2020-01-28 Wildcat Discovery Technologies, Inc. Electrolyte formulations for lithium ion batteries
US10692659B2 (en) 2015-07-31 2020-06-23 Ada Technologies, Inc. High energy and power electrochemical device and method of making and using same
KR102640842B1 (en) * 2016-06-09 2024-02-27 삼성에스디아이 주식회사 Lithium battery
US10128537B2 (en) 2016-08-30 2018-11-13 Wildcat Discovery Technologies, Inc. Electrolyte formulations for electrochemical cells containing a silicon electrode
US10707531B1 (en) 2016-09-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes
US11024846B2 (en) 2017-03-23 2021-06-01 Ada Technologies, Inc. High energy/power density, long cycle life, safe lithium-ion battery capable of long-term deep discharge/storage near zero volt and method of making and using the same
WO2020124086A1 (en) * 2018-12-14 2020-06-18 Cuberg, Inc. System for an ionic liquid-based electrolyte for high energy battery
GB201916354D0 (en) * 2019-10-18 2019-12-25 Mexichem Fluor Sa De Cv Composition
KR20220107202A (en) * 2019-11-05 2022-08-02 더 스쿨 코포레이션 칸사이 유니버시티 Electrolyte, lithium sulfur secondary battery and module
US20230299362A1 (en) * 2022-03-18 2023-09-21 Sila Nanotechnologies, Inc. Electrolyte compositions for lithium-ion battery cells with anodes comprising a blend of silicon-carbon composite particles and graphite particles

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5219683A (en) * 1990-08-02 1993-06-15 Eveready Battery Company, Inc. Diol diesters and alkoxyalkylesters as solvents for nonaqueous battery electrolytes
US20010019800A1 (en) * 1998-12-10 2001-09-06 Sylvie Herreyre A rechargeable lithium electrochemical cell usable at low temperature
CN1650466A (en) * 2002-03-05 2005-08-03 坎梅陶尔股份有限公司 Electrochemical cell for a lithium ion battery with improved high-temperature stability
US20070148540A1 (en) * 2005-09-26 2007-06-28 Takanobu Chiga Nonaqueous electrolyte for secondary battery and nonaqueous electrolyte secondary battery
US20070287071A1 (en) * 2006-06-11 2007-12-13 Sanyo Electric Co., Ltd. Non-aqueous electrolyte solution for secondary battery and non-aqueous electrolyte secondary battery using the electrolyte solution
WO2010002089A1 (en) * 2008-06-30 2010-01-07 Lg Chem, Ltd. Cylindrical lithium secondary battery
WO2010004952A1 (en) * 2008-07-09 2010-01-14 ダイキン工業株式会社 Nonaqueous electrolyte solution
US20100035162A1 (en) * 2008-08-05 2010-02-11 Sanyo Electric Co., Ltd. Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery
US20100081062A1 (en) * 2007-02-20 2010-04-01 Sanyo Electric Co., Ltd. Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3444607B2 (en) * 1992-07-07 2003-09-08 三菱化学株式会社 Electrolyte for lithium secondary battery
JPH08250153A (en) * 1995-03-08 1996-09-27 Yuasa Corp Thin battery
JPH09147913A (en) 1995-11-22 1997-06-06 Sanyo Electric Co Ltd Nonaqueous electrolyte battery
JP3809662B2 (en) * 1996-01-30 2006-08-16 宇部興産株式会社 Non-aqueous secondary battery
US6492064B1 (en) 1998-06-04 2002-12-10 California Institute Of Technology Organic solvents, electrolytes, and lithium ion cells with good low temperature performance
GB9929698D0 (en) * 1999-12-15 2000-02-09 Danionics As Non-aqueous electrochemical cell
DE10111410C1 (en) * 2001-03-08 2002-07-25 Chemetall Gmbh Lithium bis(oxalato)borate electrolyte, used in electrochemical storage system or electrochromic formulation, e.g. window, contains ternary solvent system
US6787268B2 (en) 2002-09-03 2004-09-07 Quallion Llc Electrolyte
EP1555711B1 (en) 2002-10-22 2011-12-21 Mitsubishi Chemical Corporation Nonaqueous electrolytic solution and nonaqueous electrolyte secondary battery containing the same
JP5235437B2 (en) * 2007-02-20 2013-07-10 三洋電機株式会社 Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery
US7722994B2 (en) * 2007-03-28 2010-05-25 Gm Global Technology Operations, Inc. Lithium-ion battery non-aqueous electrolytes
US8920981B2 (en) 2008-04-08 2014-12-30 California Institute Of Technology Lithium ion electrolytes and lithium ion cells with good low temperature performance
WO2009127901A1 (en) 2008-04-14 2009-10-22 High Power Lithium S.A. Lithium metal phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries
CN102265447B (en) * 2008-12-23 2015-05-06 陶氏环球技术有限责任公司 Battery electrolyte solutions containing aromatic phosphorus compounds

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5219683A (en) * 1990-08-02 1993-06-15 Eveready Battery Company, Inc. Diol diesters and alkoxyalkylesters as solvents for nonaqueous battery electrolytes
US20010019800A1 (en) * 1998-12-10 2001-09-06 Sylvie Herreyre A rechargeable lithium electrochemical cell usable at low temperature
CN1650466A (en) * 2002-03-05 2005-08-03 坎梅陶尔股份有限公司 Electrochemical cell for a lithium ion battery with improved high-temperature stability
US20070148540A1 (en) * 2005-09-26 2007-06-28 Takanobu Chiga Nonaqueous electrolyte for secondary battery and nonaqueous electrolyte secondary battery
US20070287071A1 (en) * 2006-06-11 2007-12-13 Sanyo Electric Co., Ltd. Non-aqueous electrolyte solution for secondary battery and non-aqueous electrolyte secondary battery using the electrolyte solution
US20100081062A1 (en) * 2007-02-20 2010-04-01 Sanyo Electric Co., Ltd. Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery
WO2010002089A1 (en) * 2008-06-30 2010-01-07 Lg Chem, Ltd. Cylindrical lithium secondary battery
WO2010004952A1 (en) * 2008-07-09 2010-01-14 ダイキン工業株式会社 Nonaqueous electrolyte solution
US20100035162A1 (en) * 2008-08-05 2010-02-11 Sanyo Electric Co., Ltd. Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106207262A (en) * 2015-05-25 2016-12-07 松下知识产权经营株式会社 Electrolyte and battery
CN105762410A (en) * 2016-04-01 2016-07-13 宁德新能源科技有限公司 Non-aqueous electrolyte and lithium-ion battery using same
CN105762410B (en) * 2016-04-01 2018-11-02 宁德新能源科技有限公司 A kind of nonaqueous electrolytic solution and the lithium ion battery using the nonaqueous electrolytic solution
CN111758180A (en) * 2017-10-31 2020-10-09 关东电化工业株式会社 Nonaqueous electrolyte solution and nonaqueous electrolyte battery
CN111758180B (en) * 2017-10-31 2023-10-20 关东电化工业株式会社 Nonaqueous electrolyte and nonaqueous electrolyte battery
CN111656595A (en) * 2018-01-30 2020-09-11 大金工业株式会社 Electrolyte solution, electrochemical device, lithium ion secondary battery, and assembly
CN111656595B (en) * 2018-01-30 2024-01-05 大金工业株式会社 Electrolyte, electrochemical device, lithium ion secondary battery and assembly
CN110611084A (en) * 2018-06-15 2019-12-24 武汉大学 Lithium-sulfur secondary battery with long cycle life and 100% coulombic efficiency
CN110611084B (en) * 2018-06-15 2023-03-24 武汉大学 Lithium-sulfur secondary battery with long cycle life and 100% coulombic efficiency
CN110534807A (en) * 2019-09-29 2019-12-03 河南省法恩莱特新能源科技有限公司 A kind of LiNi0.5Mn1.5O4Positive lithium-ion battery electrolytes and preparation method
WO2023179456A1 (en) * 2022-03-25 2023-09-28 深圳新宙邦科技股份有限公司 Non-aqueous electrolyte and secondary battery

Also Published As

Publication number Publication date
US9472813B2 (en) 2016-10-18
JP5886870B2 (en) 2016-03-16
CN103262329B (en) 2016-02-10
WO2012082760A1 (en) 2012-06-21
KR20130130775A (en) 2013-12-02
CA2821958A1 (en) 2012-06-21
US20130260229A1 (en) 2013-10-03
JP2014503964A (en) 2014-02-13
EP2652832A1 (en) 2013-10-23

Similar Documents

Publication Publication Date Title
CN103262329B (en) Containing some based on the cell electrolyte solution of the solvent of ester and the battery containing such electrolyte solution
EP2382683B1 (en) Battery electrolyte solutions containing aromatic phosphorus compounds
CN104011914B (en) Lithium storage battery electrode containing lithium oxalate
CN102823051B (en) Battery electrolyte solutions containing phosphorus-sulfur compounds
CN103380530A (en) Nonaqueous electrolyte and nonaqueous-electrolyte secondary battery using same
US9865900B2 (en) Solid electrolyte interphase film-suppression additives
CN111373593B (en) Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same
CN110998958B (en) Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same
JP2006216361A (en) Electrolytic solution for lithium battery
US20170187071A1 (en) Lithium battery electrolyte solution containing ethyl (2,2,3,3-tetrafluoropropyl) carbonate
US20170187072A1 (en) Lithium battery electrolyte solution containing (2,2-difluoroethyl) ethyl carbonate
JP2007059192A (en) Nonaqueous electrolyte secondary battery and its manufacturing method
JP2002280061A (en) Nonaqueous electrolyte and lithium secondary battery using the same
JP4146646B2 (en) Flame retardant electrolyte and non-aqueous electrolyte secondary battery
WO2012174704A1 (en) Battery electrolyte solutions containing aromatic phosphite compounds
WO2016085666A1 (en) Solid electrolyte interphase film-suppression additives
EP4123781A1 (en) Non-aqueous electrolyte and energy device using said non-aqueous electrolyte
US20170187062A1 (en) Lithium battery electrolyte solution containing methyl (2,2,3,3,-tetrafluoropropyl) carbonate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160210

Termination date: 20181213